Attractants for yellow jackets (vespula spp.: vespidae)

ABSTRACT

The insect attractants of the present invention are highly specific for yellow jackets (Vespula spp.), attracting few other insects and no beneficial species such as honey bees. These attractants are organic esters having a total of from nine to 12 carbon atoms, and they have at least one center of unsaturation, as exemplified by cis-3-hexenyl butyrate and 2-methylpentyl crotanate, or an alicyclic radical as in 4-methylcyclohexyl butyrate. The ester, 2,4-hexadienyl butyrate, was outstanding in field tests. Incorporated into compositions containing an insecticide, chemosterilant or other control agent, the attractants provide an improved means of reducing or eliminating populations of yellow jackets.

United States Patent Eddy et al.

[4 1 Oct. 14, 1975 [75] Inventors: Gaines W. Eddy, Mission, Tex.;

Harry G. Davis, Fresno, Calif.; Morton Beroza, Silver Spring; Terence P.McGovern, Bowie, both of Md.

[73] Assignee: The United States of America as represented by theSecretary of Agriculture, Washington, DC.

[22] Filed: Oct. 19, 1973 [21] Appl. No.: 408,036-

Related US. Application Data [62] Division of Ser. No. 246,024, April20, I972, abandoned, which is a division of Ser. No. 857,611, June 27,1969, abandoned, which is a division of Ser. No. 623,154, Dec. 29, 1966,Pat. No. 3,485,868.

[52] US. Cl. 424/84; 424/314 [51] Int. Cl. A01N 17/14; AOlN 9/24 [58]Field of Search 424/84, 314, 311

[56] References Cited UNITED STATES PATENTS 3,072,526 1/1963 Butenandt424/84 FOREIGN PATENTS OR APPLICATIONS 621,007 2/1963 Belgium PrimaryExaminer-V. D. Turner Attorney, Agent, or Firm-M. Howard Silverstein;Max D. Hensley; William E. Scott [57] ABSTRACT The insect attractants ofthe present invention are highly specific for yellow jackets (Vespulaspp.), attracting few other insects and no beneficial species such ashoney bees. These attractants are organic esters having a total of fromnine to 12 carbon atoms, and they have at least one center ofunsaturation, as exemplified by cis-3-hexenyl butyrate and 2methylpentyl crotanate, or an alicyclic radical as in 4-methylcyclohexylbutyrate. The ester, 2,4- hexadienyl butyrate, was outstanding in fieldtests. Incorporated into compositions containing an insecticide,chemosterilant or other control agent, the attractants provide animproved means of reducing or eliminating populations of yellow jackets.

7 Claims, No Drawings ATTRACTANTS FOR YELLOW JACKETS (VESPULA SPP.:VESPIDAE) A non-exclusive, irrevocable, royalty-free license in theinvention herein described, throughout the world for all purposes of theUnited States Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This application is a division of application Ser. No. 246,024, filedApr. 20, 1972, now abandoned, which is a division of application Ser.No. 857,611, filed June 27, 1969, now abandoned, which is a division ofapplication Ser. No. 623,154, filed Dec. 29, 1966, now US. Pat. No.3,485,868.

This invention relates to compounds useful for attracting yellow jackets(Vespula spp.), which are insects of medical and pestiferous importance.The invention relates further to combinations of these attractants withinsect control agents, such as insecticides, chemosterilants, and thelike to provide the respective attractant compositions.

According to one authority hymenopterous insects caused almost 50% ofthe 460 deaths attributed to venomous animals in the United Statesbetween 1950 and 1959. Of these almost 5% were caused by yellow jackets. However, these fatalities represent only a small percentage of thenumber of persons attacked, hospi talized, or otherwise imposed upon bythese insects. Inasmuch as attractants have proved very useful as an aidin controlling other insect pests, it is anticipated that attractantswould be useful similarly in combating yellow jackets. For example, theattractant may be used in a trap, poisonous bait, or distributed with atoxicant on a carrier. One of the especially desirable features of usingattractants for control is that very little of the insecticide or insectcontrol agent is required. The use of the instantly claimed attractantswould be most efficient because such problems as do arise with yellowjackets often occur in a localized area. Attractants have a furtheradvantage in that they can be used to lure the insects to their death,while at the same time, offering practically no chemical hazards to man,animals, or plants. The attractants herein described have still anotherdesirable feature, in that they are highly specific for yellow jackets.They attracted few other insects, most of which were consideredaccidental catches, and no beneficial species such as honey bees.

An object of the present invention is to provide attractants for use inreducing or eliminating populations of yellow jackets. Another object isto provide yellow jacket attractants that are highly specific for thisinsect. A further object is to provide chemical yellow jacketattractants suitable for inclusion in compositions with insecticides,chemosterilants, and other insect control agents. Other objects will beapparent upon inspection of the specification and claims.

We have discovered that certain organic esters are highly specific asattractants for yellow jackets.

According to the present invention an attractant for yellow jacketscomprises an ester having an alcohol moiety (part) and an acid moiety,the ester having a total of from nine to 12 carbon atoms per molecule,in which ester at least one of the moieties is aliphatic with at leastone center of unsaturation or is alicyclic.

In a preferred embodiment of the invention the alcohol moiety of theorganic ester is derived from an unsaturated aliphatic alcohol havingfive to seven carbon atoms, especailly the 2,4-hexadienyl andcis-3-hexenyl groups (radicals or is an alicyclic group such ascyclohexyl or 4-methylcyclohexyl.

In another embodiment of the present invention the center ofunsaturation is in an aliphatic acid moiety of the ester, as in certainacrylates, methacrylates, crotonates, sorbates, and heptynoates. Theester can also have unsaturation in both the alcohol and acid moieties,as in 2,4-hexadienyl esters of crotonic or tiglic acid.

The attractiveness for yellow jackets of the esters of the presentinvention was demonstrated by practical field tests. In a typicaltest,'about 0.25 gram of the ester to be evaluated and 2 ml of acetonewere placed in the bottom of a pint glass jar which was rotated todistribute the compound. The jar was capped with an inverted screen conehaving a [2-inch diameter hole at the apex of the cone. The jars werethen placed in the field l to 2 feet apart on boards positioned about 3feet off the ground. Tests were usually started at noon and terminated24 or more hours later. Insects responding to the candidate luresentered the /2-inch orifice and were then unable to escape the trap.

Other aspects of testing, such as varying the amount of attractant, thetime factors, and use of controls, are illustrated by the field testdata presented in Table 1.

TABLE I Results of field tests on the attractiveness of materials toyellow jackets vespula pensylvanica. Straight-sided pint glass jars usedas traps except as noted.

Amount per trap (mL) Chemical No. of yellow jackets caught (cumulative)after indicated hr.

Test of Sept. 15, 1964 2,4-Hexadienyl butyrate 0.5

2,4-Hexadienyl propionate 2,4-Hexadienyl isobutyrate Controls: l/acetone water 2,4-Hexadienyl butyrate 0 5 2,4-Hexadienyl propionate 0.52,4-Hexadienyl isobutyrate 0.5 n-Butyl sorbate 0 5 Sorbic acid 2 TABLE lContinued Results of field tests on the attractiveness of materials toyellow jackets vespula pensylvanica. Straight-sided pint glass jars usedas traps except as noted.

Amount per No. of yellow jackets caught Chemical trap (ml.) (cumulative)after indicated hr.

Amyl acetate 0.05 0 0 Controls: acetone 0 0 0 water 0 0 0 Test of Oct.15, 1964 4/ (pint jars) Butyric acid 0.25 0 Propionic acid 0.25 02,4-l-lexadienyl butyrate 0.25 94 Control: acetone 0 (gallon jars)Butyric acid 0.25 0 Propionic acid 0.25 O 2,4-Hexadienyl butyrate 0.2539 Control: acetone 0 Test of Oct 22, 1964 5/ (pint jars)2,4-l-lexadienyl butyrate 0.5 58 2,4-Hexadienyl acetate 0.5 02,4-Hexadienyl chloroacetates 0.5 1 2,4-Hexadienyl o-ethoxybenzoate 0.50 2.4-Hexadieny1 p-toluate 0.5 0 Control: acetone 0 Test of Oct. 6, 19642,4-Hexadienyl butyrate 0.25 1 l 0.025 l 2.4-Hexadienyl propionate 0.250

0.025 0 2,4-l-lexadienyl isobutyrate 0.25 7

0.025 0 n-Butyl sorbate 0.5 0 Control: acetone 0 Test of Oct 8, 1964n-Butyl sorbate 0.5 5 12 12 Control: acetone 0 0 0 Test of Oct. 13, 1964n-Butyl Sorbate 0.25 3 3 7 2,4-Hexadien-1-ol 0.25 0 0 0 Sorbaldehyde0.25 0 0 1 2,4-Hexadienyl butyrate 0.25 33 2,4-l-lexadienyl-p-anisate0.25 0 0 0 Control: acetone 0 0 0 1/ Two ml. of solvent was added to allcontrol jars since this amount was used with attractants; water was usedas a second control in some tests. 2/ 500 mg.

3/ Removed from test after 4 hours due to high attractiveness. 4/ Bothsize jars equipped with inverted screen cones. 5/ Jars equipped withsolid metal lids with 'h-in. hole in center.

TABLE 2 Physical constants of new esters tested as attractants foryellow jackets.

Elemental Analyses Ester B.p. Mol. Theory (C/mm) n Form. C %H %C2,4-Hexadienyl butyrate l 10-1 1/ 18 1.4696 C H O, 71.39 9.59 71.34 9.522,4-Hexadienyl crotenzate 7811.5 1.4937 C H O, 72.26 8.49 72.05 8.302,4-1-1exadienyl 2-methy1butyrate 57/0.6 1.4646 C I-1 0, 72.49 9.962,4-l-lexadienyl valerate 125/20 1.4648 C I-1 0, 72.49 9.96 72.15 10.062,4-Hexadienyl isobutyrate 48-9/1 1.4654 C H O 71.39 9.59 71.77 9.642,4-l-lexadienyl propionate 120/28 1.4734 C H O, 70.10 9.15 70.14 9.342,4-l-lexadienyl isovalerate 85-6/3.5 1.4638 C H O 72.49 9.96 72.17 9.872,4-Hexadienyl pivalate 49/0.04 1.4576 C H O 72.49 9.96 72.76 9.842,4-l-lexadienyl tiglate 72/0.04 1.4938 C H O, 73.30 8.95 2,4-Hexadienylchloroacetate 77-8/1 1.4979 C,H, CIO, .02 6.35 2,4-Hexadienyl acetate94-5/31 1.4731 C l-1 ,0, 68.54 8.63 68.84 8.64 2,4-Hexadienyl hexanoate140/20 1.4675 C A-1 0; 73.43 10.27 72.71 10.18 2,4-Hexadienyl3-methylcrotonate /0.4 1.4966 C H O, 73.30 8.95 73.65 9.26 cis-3-Hexenylbutyrate 96/20 1.4287 1 m g 70.54 10.66 70.24 10.81 4-Methylcyc1ohexylbutyrate 109/20 1.4379 n O, 71.69 10.94 71.43 11.13l-Methyl-Z-methylallyl butyrate 83/25 1.4226 C .H O, 70.54 10.66 70.2210.58 Cyclohexyl butyrate 2/ 99/20 1.4391 c n o, 70.54 10.66 70.30 10.621-Methy1-3-butyenyl butyrate 69/18 1.4158 c.l-l.,o, 69.19 10.32 69.0510.35 l-Propyl-Z-propynyl butyrate 88/20 1.4243 C H O 71.39 9.59 71.279.50 1,1,2-Trimethyl-3-buteny1 butyrate 86/20 1.4284 C M O 71.69 10.9471.58 10.82 l-lsopropylallyl butyrate 76/33 1.4196 C H o 70.54 10.6670.68 10.60 2-Dimethyl-2-butenyl butyrate 81/19 1.4258 C H O, 70.5410.66 70.02 10.53 1-Propyl-3-butenyl butyrate 94/19 1.4243 C H O 71 .6910.94 71.43 10.50 3-Methylcyclohexyl butyrate 107-8/20 1.4376 C H o71.69 10.94 71.15 11.23 l-Propylallyl butyrate 82-3/19 1.4200 C H O,70.54 10.66 70.62 10.57 1,1-Dimethyl-3-butenyl butyrate 81-82/19 1.4260C H O 70.54 10.66 70.34 10.57 1-Ethyl-1-methyl-2-butenyl butyrate l14-6/40 1.4286 C H O 71.69 10.94 71.50 10.76 l-Pentylallyl butyrate111/20 1.4267 C H O, 72.68 11.18 72.81 11.26

TABLE 2 Continued Physical constants of new esters tested as attractantsfor yellow jackets.

Elemental Analyses Ester B.p. Mol. Theory Found ("C/mm) n Form. C %H %CYrH 1,1-Dimethyl-2-oxo-propyl butyrate 94-5/20 1.4208 C H O 62.76 9.3663.19 9.62 1.1-Dimethylallyl butyrate 61/21 1.4160 C H O, 69.19 10.3268.71 10.40 l-Ethyl-2-propynyl butyrate 75-6/20 1.4232 g 0 70.10 9.1570.37 9.42 l-Ethyl-Z-butenyl butyrate 84-5/20 1.4238 CmHmOz 70.54 10.6670.71 10.63

x] The compounds for which data is omitted could not be purifiedsufi'iciently for a good elemental analyses. 21 Although previouslyreported [W. L. Hoffman. Riechstofie u. Aromen 9, 273-6 (1959)] ourrefractive index was different. The compound was therefore analyzed.

Many of the esters evaluated as attractants for yellow jackets weresynthesized for use in the field tests. The esters were prepared byreacting an alcohol with an acid chloride using pyridine as ahydrochloric acid scavenger. A typical procedure is illustrated by thefollowing description of the preparation of 2,4-hexadienyldl-2-methylbutyrate:

dl-Z-Methylbutyryl chloride, l2.l grams, was added dropwise, to an icecoldsolution of 2,4-hexadien-1-ol, 9.8 grams and pyridine, 8 grams, in100 ml.- of benzene. The solution was stirred vigorously during theaddition and for 1 hourafter the. addition was completed. Ether wasadded (ca. 150 ml.) and the organic layer was extracted with water untilthe wash was neutral to litmus paper. The organic layer was dried overmagnesium sulfate, filtered, and the ether and benzene removed underreduced pressure'(water pump). After the addition of a small amount ofhydroquinone the crude ester was distilled under high vacuum togive 13.4grams of product which had the following constants: b.p. 5657/0.6.mm,' n1'.4646.

Chemical and physical constants ofv compounds not previously describedin the literature are presented in Table 2. Also, thepurity of theesters was checked by gas chromatography. .1

While the attractants of the present invention are not indicated toattract other insects, they are generally applicable to yellow jackets;As shown in Table 3, the species Vespula atropilosa, Vespulapensylvanica and Vespula vulgaris were collected in the area ofWillamette Valley of Oregon and in Kamloops and Peter Hope Lake,B.C.,-Canada. In addition, three otherspecies of Vespula were collectedin tests conducted in the eastern part of the UnitedStates.

I TABLE 3* Data pertaining to species 01 yellow jackets attracted to2.4-h'exadieny'l butyrate during tests conducted over a three weekperiod.

l/ Collections on many dates at this site.

As evident from the data, particularly the field tests of Sept. 15 andOct. 1, of Table l, the 2,4-hexadienyl esters of butyric, isobutyric andpropionic acids are po tent attractants for yellow jacketsfln these andother field tests, 2,4-hexadienyl butyrate was the most effectiveattractant. For purposes of rating the materials tested. 2,4-hexadienylbutyrate has been assigned a value of and the other compounds have beenrated in comparison with it.

In Table 4, which summarizes data regarding a series of 2,4-hexadienylesters, the attractiveness rating of each ester was determined bydividing the number of yellow jackets caught in traps containing thatester by the number caught in traps containing 2,4-hexadienyl butyrateunder otherwise similar test conditions and then multiplying by 100.

The data of Table 4 shows that in the 2,4-hexadienyl series the acidmoiety should contain three to five carbon atoms, a total of nine to l 1carbon atoms per mole cule of ester. Tables 5 and 6 contain other estersin which unsaturation is present or which havean alicylic group. Theeffective yellow jacket attractants of these tables have from nine to 12carbon atoms, usually 10 or 1 1, per ester molecule. The most potentattractants having unsaturation in the alcohol moiety are 2,4-hexadienyl butyrate and cis-3-hexenyl butyrate, both containing a totalof 10 carbon atoms. This number of carbon atoms is also contained inthebest of the esters having an unsaturated acid moiety, 2 -methylpentylcrotonate. The pentyl and isopentyl esters of 2-heptynoic acid (Table 6,Nos. 3 and 5) having 12 carbon atoms in the'ester, are also among thebetter attractants.

TABLE Relative attractiveness to yellow jackets of esters in which thealcohol moiety is unsaturated or slicyclic.

l/ 24-Hour test; 2.4-hexadienyl butyrate 100.

TABLE 6 Relative attractiveness to yellow jackets of esters in which theacid moiety is a (LB-unsaturated or alicyclic Some of the compoundscontain centers of unsaturation in both the alcohol and acid moieties,as in 2,4- hexadienyl crotonate, 3-butynyl 2-heptynoate or 2,4-hexadienyl tiglate (Table 6, Nos. 2, 4 and l 1). Others havecombinations of a center of unsaturation and an alicylic group, as inl-ethynylcyclohexyl acetate (Table 5, No. 6), cyclohexyl crotonate(Table 6, No. 9). or allyl cyclohexanecarboxylate (Table 6, No. 10).While these are active compounds, they are not as effective yellowjacket attractants as many esters containing a sole unsaturatedaliphatic radical in the molecule.

The esters of the present invention are highly specific for yellowjackets. None of the various species of beneficial insects such as honeybees were caught by or seen near any of the materials tested.

These yellow jacket attractants can be formulated with materialscommonly used in insect control art. such as baits, carriers,insecticides. chemosterilents, and other additives. Insecticides foryellow jackets useful in baits are compounds such as dimethyl (2,2,2-trichlorol -hydroxyethyl) phosphonate. 2 .2-

dichlorovinyl dimethyl phosphate. and 1.2-dibromo- 2.2-dichloroethyldimethyl phosphate. The use of slow acting insecticides or ofchemosterilantsin the attractant composition allowsthe yellow jacket toreturn to the nest, providing a more effective means of controllingyellow jacket population than trapping.

We claim:

l. A method of attracting yellowjacket wasps (Vespula spp) comprisingexposing said wasps to an effective attractant amount of an ester havingan alcohol moiety and an acid moiety and having a chain length of from10 to 12 carbon atoms, said alcohol moiety being derived from asaturated aliphatic hydrocarbon alcohol containing from five to sixcarbon atoms and said acid moiety being derived from an acid selectedfrom the group consisting of alkenoic and alkynoic acids each containingfrom four to seven carbon atoms.

2. The method of claim I in which the ester is 2- methylpentylcrotonate.

3. The method of claim 1 in which the ester is pentyl Z-heptynoate. a 4.The method of claim 1 in which the ester is isopentyl Z-heptynoate.

5. A method of attracting yellowjacket wasps (Vespula spp.) comprisingexposing said wasps to an effective attractant amount of an ester havingan alcohol moiety and an acid moiety and having a chain length of from10 to 1 1 carbon atoms, said alcohol moiety being derived from anunsaturated aliphatic hydrocarbon alcohol containing from four to sixcarbon atoms and said acid moiety being derived from an acid selectedfrom the group consisting of alkenoic and alkynoic acids each containingfrom four to seven carbon atoms.

6. The method of claim 5 in which the ester is 2,4- hexadienylcrotonate.

7. The method of claim 5 in which the ester is 3- butynyl 2-heptynoate.

1. A METHOD OF ATTRACTING YELLOW JACKET WASP (VESPULA SPP) COMPRISINGEXPOSING SAID WASPS TO AN EFFECTIVE ATTRACTANT AMOUNT OF AN ESTER HAVINGAN ALCOHOL MOIETY AND AN ACID MOIETY AND HAVING A CHAIN LENGTH OF FROM10 TO 12 CARBON ATOMS, SAID ALCOHOL MOIETY BEING DERIVED FROM ASATURATED ALIPHATIC HYDROCARBON ALCOHOL CONTAINING FROM FIVE TO SIXCARBON ATOMS AND SAID ACID MOIETY BEING DERIVED FROM AN ACID SELECTEDFROM THE GROUP CONTAINING OF ALKENOIC AND ALKUNOIC ACIDS EACH CONTAININGFROM FOUR TO SEVEN CARBON ATOMS.
 2. The method of claim l in which theester is 2-methylpentyl crotonate.
 3. The method of claim 1 in which theester is pentyl 2-heptynoate.
 4. The method of claim 1 in which theester is isopentyl 2-heptynoate.
 5. A method of attracting yellowjacketwasps (Vespula spp.) comprising exposing said wasps to an effectiveattractant amount of an ester having an alcohol moiety and an acidmoiety and having a chain length of from 10 to 11 carbon atoms, saidalcohol moiety being derived from an unsaturated aliphatic hydrocarbonalcohol containing from four to six carbon atoms and said acid moietybeing derived from an acid selected from the group consisting ofalkenoic and alkynoic acids each containing from four to seven carbonatoms.
 6. The method of claim 5 in which the ester is 2,4-hexadienylcrotonate.
 7. The method of claim 5 in which the ester is 3-butynyl2-heptynoate.